Double-hybrid density functionals with long-range dispersion corrections: higher accuracy and extended applicability
Abstract
The objective of this work is the further systematic improvement of the accuracy of Double-Hybrid Density Functionals (DHDF) that add non-local electron correlation effects to a standard hybrid functional by second-order perturbation theory (S. Grimme, J. Chem. Phys., 2006, 124, 034108). The only known shortcoming of these generally highly accurate functionals is an underestimation of the long-range dispersion (van der Waals) interactions. To correct this deficiency, we add a previously developed empirical dispersion term (DFT-D) to the energy expression but leave the electronic part of the functional untouched. Results are presented for the S22 set of non-covalent interaction energies, the G3/99 set of heat of formations and conformational energies of a phenylalanyl-glycyl-glycine peptide model. We furthermore propose seven hydrocarbon reactions with strong intramolecular dispersion contributions as a benchmark set for newly developed density functionals. In general, the proposed composite approach is for many chemically relevant properties of similar quality as high-level coupled-cluster treatments. A significant increase of the accuracy for non-covalent interactions is obtained and the corrected B2PLYP DHDF provides one of the lowest ever obtained Mean Absolute Deviations (MAD) for the S22 set (0.2-0.3 kcal mol(-1)). Unprecedented high accuracy is also obtained for the relative energies of peptide conformations that turn out to be very difficult. The significant…
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